Process for treatment of proteinaceous materials



United States Patent Oflice 3,523,750 Patented Aug. 11, 1970 3,523,750PROCESS FOR TREATMENT OF PROTEINACEOUS MATERIALS Giuliana C. Tesoro,Dobbs Ferry, N.Y., assignor to J. P. Stevens & Co., Inc., New York,N.Y., a corporation of Delaware No Drawing. Continuation-in-part ofapplication Ser. No. 569,016, Aug. 1, 1966, which is acontinuation-in-part of application Ser. No. 481,094, Aug. 19, 1965.This application Nov. 8, 1968, Ser. No. 774,508

Int. Cl. D06n 13/48 U.S. Cl. 8-127.6 26 Claims ABSTRACT OF THEDISCLOSURE This invention concerns a novel process for modifyingproteinaceous substrates comprising treating said substrates withpolyfunctional aziridine reagent, and heating the treated substrateuntil the desired modification takes place.

The present invention is a continuation-in-part of my copendingapplication Ser. No. 569,016, filed Aug. 1, 1966 now abandoned, which isa continuation-in-part of my application Ser. No. 481,094, filed Aug.19, 1965, now abandoned.

The present invention relates to novel processes for treatment ofproteinaceous materials and more particularly processes for enhancingthe properties and characteristics of textiles containing wool fibersand improved products obtained thereby.

Various methods have been devised for the treatment of textile fabricscontaining wool in order to improve certain properties thereof.Particularly important to the wool industry are methods and compositionsto bring about improvements in the dimensional stability and the feltingcharacteristics of textiles containing wool fibers. Although manymethods have been developed for W001 treatment, relatively few givesatisfactory results from the standpoint of improvement in dimensionalstability and felting. Moreover, prior known methods frequently maydeleteriously and adversely aflfect the appearance, handle, strength andother properties of the woolen textiles.

Accordingly, it is the object of the present invention to provide novelprocesses for imparting improved properties to proteinaceous materials,particularly wool-containing textile materials, which overcome theshortcomings and disadvantages associated with prior methods andcompositions.

It is a further object of the present invention to provide novelprocesses for imparting excellent properties and characteristics towool-containing textiles which avoid the drawbacks of prior methods andcompositions.

It is a further object of the present invention to pro vide novelprocesses for imparting to wool-containing textile material excellentproperties of dimensional stability and resistance to felting.

It is a further object of the present invention to provide woolentextiles having improved properties, particularly dimensional stability.

It is a further object of the present invention to provide processes fortreating wool-containing textile materials without. adversely affectingthe appearance, handle, strength and other desirable properties of thetextile.

It is a further object of the present invention to provide processes fortreating wool-containing fabrics which have desirable surface appearanceafter laundering, particularly minimal fuzziness.

In attaining the above objects, one feature of the present inventionresides in imparting excellent properties and characteristics toproteinaceous materials by treating textile materials containing woolfibers with a selected group of polyfunctional compounds of a specifiedstructure whereby the improvements in dimensional stability and otherphysical properties are achieved without adversely affecting theappearance, hand, strength and other desir able properties of thetextile.

More particularly, a proteinaceous textile substrate such as wool andits blends is treated with a solution of polyfunctional compositionrepresented by the structural formula:

o H H 0 wherein A is selected from the group consisting of Az,

NHC,,H ,,Az, and OC,,H Az

a is an integer from 1 to 4, m is an integer from 2 to 4, Az is N R -OCR R1; R2

where R R R are selected from the group consisting of H and alkyl havingfrom 1 to 4 carbon atoms,

J which has the valence of m is the residue of a polyol having at least2 to 8 hydroxyl groups,'after 2 to 4 hydroxyl groups have been removed,and

Q is selected from the group consisting of divalent aromatic andalkyl-su-bstituted aromatic groups having 6 to 18 carbon atoms,

to deposit an amount sufficient to obtain the enhancement of propertiessought, dried and cured at elevated temperatures until the properties ofthe substrate are enhanced.

While all of the above polyfunctional compositions function effectivelyas modifiers and enhancers of proteinaceous substrates, as in any largegroup, some members of the group, for various reasons, function moreeffectively than the others and for this reason are preferred. Thus, inthe instant case, a more restricted group of compositions includedwithin the above broad group, cornprise the preferred compositions ofthis invention. These compositions are included within the structuralformula:

wherein m is a number from 2 to 4, A2 is R1 Ree-Me R and R areindependently selected from the group consisting of H and alkyl havingfrom 1 to 4 carbon atoms,

3 I which has the valence of m is the residue of an aliphatic oralicyclic polyol having from 2 to 4 hydroxyl groups after 2 to 4hydroxyl groups have been removed, and

Q is methylphenylene.

In the preferred process embodiment a woolen or wool blend substrate iscontacted with an amount of one or more of the preferred treatingagents, in the form of a liquid solution, sulficient to deposit amodifying or enhancing amount of agent and cured until the desiredenhancement of properties is obtained. Ordinarily the concentration oftreating agent required varies between about 0.25 to by weight with thetrue upper limit determined primarily be economics. The mode ofapplication is not critical; padding, spraying, dipping or the likebeing applicable. Depending upon the initial concentration of agentutilized, the pickup varies between about 50% to about 300%. Normallythe treated substrate is dried and cured at about 100 C. to 200 C. forabout 3 to 6 minutes, longer times being acceptable.

A further feature of the present invention resides in treatingWool-containing textile materials with a group of polyaziridinylcompounds and with selected co-reactants in order to further enhance andimprove the dimensional stability and other physical properties of thetextile without adversely affecting the appearance, hand, strength andother desirable properties thereof.

A more specific feature of the present invention resides in treatingWool-containing textile materials according to a process hereinafterdefined with a certain group of relatively high molecular weightpolyaziridinyl compounds in the presence of selected polybasic acids ofpolyamino compounds whereby excellent properties are imparted to thetextile.

The above, as well as other objects, features and advantages of thepresent invention will become apparent from the following detaileddescription thereof.

According to the present invention, novel processes are provided wherebywool-containing textile materials, particularly Woven and knittedfabrics containing wool fibers, are treated with selected polyfunctionalcompounds to impart dimensional stability and other desirable propertiesto the textile product without substantially adversely affecting theappearance, handle, strength and other mechanical properties thereof.

It has been observed that the dimension properties of wool-containingtextile materials are considerably enhanced as a result of the novelprocesses of the present invention and further that the desiredproperties are obtained without causing undesirable discoloration,harshening or other undesirable side effects. Moreover, in accordancewith a further aspect of the present invention, novel processes areprovided whereby an enhancement in the physical properties ofwool-containing textile materials, particularly dimensional stability,are obtainedwhen the above-defined aziridine compounds are used inconjunction with co-reactants to be defined hereinafter which bringabout an even greater improvement than was heretofore possible.

A detailed description of the substituents included within the formulaedefining the polyfunctional compounds of this invention follows:

The compounds that are preferred for the present invention arepolyfunctional compounds defined by Formula I, supra.

Aziridinyl compounds as defined by the symbol A2 in the various formulaswhich are suitable for purposes of the present invention may be obtainedby several means such as, for example, the methods disclosed in BritishPat. No. 919,861, the entire disclosure of which is relied on andincorporated herein by reference. Briefly described, the aziridinylcompounds defined by Formula I, supra, may be prepared by reacting anorganic polyisocyanate with, preferably, an organic compound containingat least two hydroxyl groups to produce an intermediate having at leasttwo isocyanate groups. Then the intermediate compound is reacted with a1,2-alkylenimine to obtain the desired product. It has been determinedthat compounds falling Within the scope of the Formula 1, supra areexceptionally suitable for the treatment of wool-containing textilematerials. It will be apparent from a consideration of the compoundsencompassed by the present invention that the average molecular weightof the preferred compounds will range from about 1000 to about 6000.Such compounds are commercially available or can be prepared by knownmethods from commercially 7 available raw materials.

GROUPS REPRESENTATIVE OF Q Name: Composition Phenylene (o, m, or

P) s 4 Methylphenylene (various isomers such as 4-methyl-m-phenylone)-C6H3(CH3)- (o, m, or p)-Phenylenedimethylene H CC H OH Biphenylylene CH C H Methylenedi-(o, m, or

p)-phenylene C H CH C H Benzylphenylene C H (CH C H Naphthylene --C 'HThe residue I can be (a) divalent, (b) trivalent, or (c) tetravalent.

(a) Illustrative of the residue J in the form of a divalent radical arethe following:

(II) (CH where x is a number from 1 to 100.

(III) (C,,H ,,O) C H where a is a number from 1 to 4, and x is a numberfrom about 1 to about 100, preferably from about 5 to about 40.

(IV) (CH CH=CHCH which is derived from polybutadiene, wherein theaverage degree of polymerization, u is between about 6 and about 100.

which is one kind of linear polyester radical, where n is 2 to 6, andthe average value of v is between about 3 and about 80.

which is another kind of linear polyester radical, where nis2to 6, qis3to5,andris2to 35.

where a is 1 to 4; x and y independently are 1 to and L is a divalentalicyclic radical of 3 to 20 carbon atoms, C to C alkylene, or C to Calkylene having the chain interrupted by one to ten groups in which R isH or alkyl having 1 to 5 carbon atoms.

In the general formula: I is derived from a polyol J(-OH) having amolecular weight between about 500 and about 5,500.

For instance, suitable divalent radicals of the type rep resented forFormula VII are provided by condensation products of the alkoxylate typewhich can be formed from any of the following starting compounds HOLOH,v

which are given by way of example, by

(A) Ethoxylation with approximately 10, to moleparts of ethylene oxide,

In carrying out the present invention, the wool-containing textilematerial which may be in any suitable form such as fiber, yarn or fabricmay be treated with the polyfunctional compounds defind by Formula I,generally by impregnation with a solution thereof.

The solvent vehicle may be aqueous or non-aqueous. The treating mixtureof solvent and polyfunctional compound may be in the form of a solution,suspension, emulsion or the like. The textile material may be sprayed,padded, immersed, dipped, brushed or similarly contacted with thepolyfunctional compound, thereafter dried and cured. Exposure toelevated temperature may be used to insolubilize the polyfunctionalcompound. Alternatively, the textile, after being contacted with thepolyfunctional compound may be permitted to stand for a brief period soas to achieve insolubilization.

If desired, the treated wool-containing textile material may thereafterbe washed to remove residual soluble chemicals which may interfere oradversely affect the properties of the final product. Excellentdimensional stability is imparted to woolen textiles treated in theaforementioned manner. When laundered by conventional procedurescommonly used for cotton or hydrophobic fibers, the woolen textilematerials treated in accordance with the present invention as well asgarments made from such woolen textile materials do not exhibitnoticeable felting, fuzzy appearance, shrinkage or other undesirableproperties which would deleteriously affect the final quality of thegarment.

The present invention constitutes a considerable advance over what hasgone heretofore inasmuch as the treatment with the selectedpolyfunctional compounds does not deleteriously alter the color, hand orother aesthetic properties of the woolen textile and, moreover, does notsubstantially adversely impair the tensile strength, tear strength,abrasion resistance and other important properties of the textilematerial.

In accordance with a further preferred aspect of the present invention,textile materials containing wool are treated with the aziridinecompounds represented by the Formula I supra in combination with thecoreactants as defined hereinafter to achieve even greater enhancementof the dimensional stability and other desirable properties of thetextile products. Suitable co-reactants are polybasic acids andpolyamine compounds particularly saturated aliphatic dicarboxylic acidscontaining from 2 to 12 carbon atoms and polyalkylenepolyaminescontaining, for example, from 4 to 20 carbon atoms and 2 to 5 nitrogenatoms. Representative examples of acids include succinic acid, adipicacid, sebacic acid, citric acid, tartaric acid, polyacrylic acid, andthe like. Examples of polyamines include diethylenetriamine,tetraethylenepentamine, hydroxyethylethylenediamine, polyethyleneiminesof wide molecular weight range, 1,3-diaminopropane, 1,6-diaminohexane,and the like.

In general, it has been observed that the coreactants will accelerateinsolubilization of the polyfunctional compound in or on wool and willdrive the polymerization reaction to completion in a shorter period oftime. In addition, it has been observed that in certain respects theresulting properties of the textile are superior to that treated withthe polyfunctional compound alone. It is, however,

to be noted that the invention does not require the presence ofco-reactants in order to achieve satisfactory dimensional stability orother desirable properties in the wool-containing textile.

The treating mixture containing the polyfunctional compounds as definedby the structural Formula I and a vehicle therefor may take the form ofa solution in organic solvents orwater when feasible. The compounds mayalso be applied from aqueous emulsion which can be rapidly prepared bysuitable choice of solvents and emulsifying agents. Because of theirstability at room temperature over relatively long periods of time,solutions and emulsions of the treating agents of the present inventionmay normally be stored without special precautions being necessary.

According to a further more detailed aspect of the present invention,the wool-containing textile material may be treated with theabove-defined polyfunctional compounds, either before or after dyeingbecause the treatment with aziridines does not alter or deleteriouslyaffect the dyeing properties of the woolen textiles. No adverse effectson the rate and evenness of the dyeing have been observed, even if thetreatment with the polyfunctional compound is carried out before thedyeing operation. Moreover, there is no change of shade or adverseeffect on color-fastness if the treatment with the polyfunctionalcompound is applied to the textile after the dyeing operation. Thisaspect of the invention is particularly important from a commercialstandpoint inasmuch as it allows a wider range of operating conditionsand greater flexibility in carrying out the modification of the woolentextile product.

When carrying out the process of the invention utilizing arizidinylcompounds in combination with selected coreactants as defined above, thetreatment may be carried out in a single step or in several separatesteps. Because of their nature, it is possible to use the polyfunctionalcompounds as defined herein in a single step in conjunction with otherfunctional finishes such as water and stain repellents, soil releaseagents and the like. The latter include the acrylics and their salts aswell as the fluorocarbons. The ease of formulation and application ofthe polyfunctional compounds makes them particularly suitable for use incombination with other finishes to impart permanent creasing propertiesto woolen fabrics.

No special precautions need be taken when carrying out the process ofthe present invention inasmuch as the insolubilization reaction of thepolyfunctional compound on the wool textile can take place at moderatetemperatures. It is therefore possible to obtain the desiredinsolubilization reaction even by tumble-drying procedures which areespecially desirable when the objective is the stabilization ofmanufactured woven or knitted garments which cannot be convenientlyprocessed in curing ovens at elevated temperature. Thus, the presentinvention provides a commercially feasible means for applyingshrinkproofing finishes to manufactured garments in a convenient orsimple method without requiring the use of complex equipment andprocedures.

Applicable to Wool textile materials in any form or shape, the presentinvention may be used to impart dimensional stability and other desiredproperties to wool fibers, Woolen and worsted yarn, woven or knittedfabrics and (B) Propoxylation with approximately 8 to 95 moleparts ofpropylene oxide, or

(C) Alkoxylation with a proportionate mole ratio of higher or mixedalkylene oxides.

alkyl having 1 to 5 carbon atoms, and L is CH2CH2N(R)CH2CH2.

When trivalent, the residue J is the radical remaining upon removal of 3hydroxyls from a polyol higher in degree than a diol. Examples of theresidue J in the trivalent form are represented by the indivdualcompounds embraced within the following collective Formula VIII:

(VIII) H(CuH2a-)x 0 MO(C nHZnO-) H H(0CuH2o )Z after removal of the 3terminal hydrogen atoms, wherein the value of a is 1 to 4, while x, y,and 2, each ranging from 1 to about 100, denote mole-parts of one ormore kinds of alkylene oxide C H O condensed with a trihy- O M at 6 dricstarting compound, (HO) M, M being -a trivalent organic radical. Forinstance, a suitable trivalent radical of the type represented byFormula VIII is derived from glycerol condensed with approximatelymole-parts of propylene oxide. In that case (referring to Formula VIII)M is the radical and a is 3, while the sum of x, y, and z is 50. Otheraliphatic starting compounds of the type (HO) M which may be alkylated(as by CH CH O, C H O, and C H O) are, for example, Z-methyl1,2,3-propanetriol, butanetriols, hexanetriols,2-alkyl-2-(hydroxymethyl)-l,3-propanedio1s (especially wherein the alkylgroup has 3 or less carbon atoms), triethanolamine, and2-dimethylamino)-2-(hydroxymethyl)-1,3 propanediol.

The m-valent residue J of the formulae is also provided by thecondensation products which are alkylene oxide derivatives of manystarting compounds other than those specifically named, whether theprealkoxylated compound is of the dihydric type HO-L-OH or of thetrihydric type (HO) M. Further examples of suitable starting compoundsconforming to the types of HOL-OH and (HO) M will be found in BritishPat. No. 919,861.

Typical of the methods whereby the aziridinyl compounds may be rnade isthe procedure shown in Example XXVI which describes the reaction of apolyol and an isocyanate and the subsequent reaction with thealkylenimine.

Illustrative of the above compounds are:

garments. In general, for optimum effects to be realized, the fabriccustomarily contains appreciable proportion of wool fiber, generally 30%or more, 60 to 100% being the preferred range.

It will be apparent from the foregoing that the wool present in thetextile can be by itself or present in a blend or admixture with othernatural fibers such as cotton or with synthetic fibers such aspolyamides, polyesters, polyolefins and acrylic fibers. The exampleswhich appear hereinafter generally show the reaction condition suitablefor obtaining satisfactory results. It will be noted, however, that theoptimum conditions for processing any given fiber blend or mixture willbe determined by many factors such as concentration of reagent, time ofimpregnation, temperature, atmospheric conditions, configuration, aswell as other parameters. Conditions within the ranges discussedhereinafter will generally give satisfactory results on the textilematerials indicated although these ranges are not to be construed aslimiting the invention in any way.

For most purposes, the polyfunctional compounds employed in thisinvention are used in amount sufficient to keep shrinkage below 6% basedupon the original dimensions of the substrate. Generally, between about0.5 and 10% by weight add-on based upon the weight of the dry substrateis sufficient to keep shrinkage below the desired level. This add-on isreferred to as a modifying amount of polyfunctional compositionthroughout this application. For example, in a typical embodiment wherea 100% wool substrate is treated, add-on amounts of about 2% to about 5%based on the weight of the wool treated are preferred, although amountsoutside these ranges may be used.

In accordance with the aspect of this invention relating to thecombination of the aziridine compound and coreactant, when theco-reactant is used, the amount thereof employed should be sufficient toprovide approximately 0.5 to about 2.0 reactive groups of theco-reactant which is in the form of amino groups or carboxyl groups foreach aziridinyl group of the aziridinyl compound defined by Formula I.In other words, approximately 0.5 to about 2.0 equivalents of theco-reactant, polyamine or polycarboxylic acid, should be present foreach aziridinyl equivalent present. It has been determined that thecoreactant may be added to the treating solution which contains theaziridinyl compound of Formula I or can be applied in a separate stepeither before or after application of the aziridinyl compound.Properties and characteristics may vary somewhat depending upon thesequence of reaction; however, it has been observed that generally theorder of reactants can be varied with equally satisfactory results.

As mentioned above, the aziridinyl compound can be applied to theWool-containing textile material in any convenient manner. Generally,the aziridinyl compound is dissolved at the desired concentration in ananhydrous organic solvent such as a hydrocarbon including toluene,xylene, petroleum fractions and similar materials, halogenated solventsuch as carbon tetrachloride and perchloroethylene or any otherconvenient inert solvent in which the aziridinyl compound is soluble andwhich in itself will not adversely affect the woolen textile material ordeleteriously interfere with the insolubilization of the aziridinylcompound or interfere with the functioning of the co-reactant if any isused.

The aziridinyl compound may be applied to the woolen textile substratein the form of a self-emulsifiable concentrate which is diluted withwater to the desired concentration prior to using same. In any event,the coreactant polyamine or polycarboxylic acid may be added to thetreating solution or emulsion containing the aziridinyl compound or theco-reactant may be applied in a separate step from a solution preparedfrom the same solvent as that used in connection with the aziridinecompound, or a different organic solvent or water. When the co-reactantis applied in a separate step either before or after the treatment withthe aziridinyl compound, the solvent as that used in connection with theaziridine commaterial may be miscible or immiscible with the solventsystem from which the aziridinyl compound is applied. It has beenobserved that the pH of the treating solution may be varied within aconsiderable range. Generally, very high and very low pH ranges shouldbe avoided since degradation of the wool can occur under extremeconditions. A pH range in general of 3.0 to about 9.0 is suitable withthe range of 4.0 to 8.0 being preferred for most applications.

Methods of application of the polyfunctional compounds to the woolentextile not being critical, the treating solution can be applied by anysuitable means including padding, spraying, dipping or the like. Excesssolution is generally removed by wringing, squeezing, centrifuging orspinning. Thereafter, the woolen textile material is dried at atemperature ranging from ambient temperature to about 100 C., the rangeof 50 C. to 70 C. being particularly convenient. It is to be noted thatthe drying step is not essential to the overall efiiciency of theprocess. After drying, the treated textile is cured by allowing it tostand at ambient temperature for several hours or preferably by heatingfor a few minutes at 110 C. to about 170 C. to complete theinsolubilization reaction. The time required for the curing step varieswith the particular reagent and the concentrations employed. It will benoted that the curing duration will be dependent upon the temperature,the higher temperatures requiring less curing time. Curing cycles of 3to 15 minutes at 120 C. to 150 C. have been found to give excellentresults in the majority of situations. The above ranges are indicativeof suitable reaction conditions and are by no means considered limitingof the present invention.

Although the textile may be used without further treatment, it isgenerally preferred to wash the textile after the curing step withsuitable detergent solutions, solvent scours or by any other desirablemeans in order to remove residual soluble unreacted chemicals. .The.textile material can thereafter be dyed by conventional pro-. ceduresor subjected to other conventional chemical or mechanical finishingoperations such as shearing, topping with softeners and other textiletreatments designed to impart specific properties or behaviorcharacteristics.

The following examples are illustrative of the process of the invention.Parts are by weight unless otherwise specified. The methods used inobtaining the test data given in the examples are as follows:

Shrinkage.-Measurement after laundering according to the followingprocedure: Samples ca. 18 X 18 inches with 10 x 10-inch markingslaundered in an automatic home-type agitator washing machine at 41 C.,using a 5-lb. load, detergent (Fab or Tide) and 15 minutes suds time.Washed samples were rinsed, extracted in the washer for the full cycle,dried flat on a horizontal screen and flat-bed pressed for 5 seconds at-150 C. and conditioned for a minimum of 12 hours at 63 to 67% RH. and20-22 C. The samples were then measured for shrinkage in the warp andfilling directions.'Results reported in percent. The number oflaundering-drying cyclesis indicated by 5L or 10L, respectively.

Flex abrasion resistance.ASTM-Dl-61T. (Stoll Flex Abrader, lb. head, 2lbs. toggle). Results reported in cycles to break.

Stifiness-Cantilever procedure. ASTM-D-l388-55T. Results reported inmilligram-centimeters.

Reflectance.-ASTME9755. Photovolt Search 6104, using the greentristumulus filter.

Oil repellency.-Minnesota Mining and Manufacturing Bulletin onFluorochemical, Appendix A, pages 1-2.

610 and Measured after laundering (same washing procedure asforShrinkage) and after dry cleaning (Minnesota Mining and ManufacturingTest Method for laboratory dry cleaning procedure, 1.0. page 4).

1 l Tensile strength.ASTM D 1682 9T, one-inch ravelled strip method.Reported in pounds.

F uzziness rating.-The hairy appearance was expressed by the followingnumerical scale after brushing the fabric for minutes on a testingmachine:

( 1) Severe fuzzing (2) Considerable fuzzing (3) Moderate fuzzing (4)Slight fuzzing (5) No (or negligible) fuzzing Fuzzing caused bylaundering was rated after machine washing at 105 F. and tumble drying(12 such cycles in Example XXII, 10 in Example XXIII).

Flat frosting rating.Variation in appearance of colored fabric caused byconcentrated localized abrasive wear. (Flexing is not used in fiatfrosting.) The AATCC Gray Scale for Evaluating Changes in Color was usedin applying the following rating scale to the descriptive meanings:

(1) Severe change (2) Considerable change (3) Moderate change (4) Slightchange (5) No (or negligible) change 12 polymer has three of thefollowing groups per molecule attached to a polypropylene ether glycolbackbone:

-o oo-rrn-Q-om i CH 3 I1IHCON/ a. The full structure is believed to be:

wherein x+y+z=50.

The solution contained 4% ITP-63A and Wasapplied to the sample by usinga laboratory padder and setting the rolls of the padder at such apressure as to obtain a wet pickup of about 110%.

The fabric sample so treated was framed at the original dimensions anddried at 65 C., then cured for 5 minutes at 135 C. in a forced-draftoven. The cured fabric was rinsed in toluene, dioxane, and finally inwater. The sample was then again framed to the original dimensions anddried. The test results obtained were as follows:

Percent shrinkage after 5L 10L Flex Wash-and-wear rating.AATCC88A-l964T, Test IICl.

Colorfastness to wash.AATCC-6 l1962.

Colorfastness to light.AATCC16A-1964.

Colorfastness to cr0cking.AAT CC8-196l.

Colorfastness t0 perspirati0n.AATCC15-1962.

Abbreviations in tables..When used individually, F means fillingdirection, and W means warp direction. OWB: On the Weight of the bath.OWF: On the Weight of the fabric. WPU: Wet pickup. OWB times WPU/ 100%:OWF.

Isocyanate content-As in a fraction of an equivalent per 100 grams:Determined by a modification of the dibutylamine procedure of W.Siefken, Liebigs Annalen der Chemie, vol. 562, page 100 (1949).

EXAMPLE I Dimensional stabilization of woolen fabric by treatment with apropylene imine-terminaied polymer of polypropylene ether glycol Asample of plain weave 100% Woolen fabric, in the ready-to-dye state, wastreated with a liquid, trifunctional, propylene imine-terminated polymerof polypropylene ether glycol (Interchemical Corp. ITP-63A) having anaverage molecular weight of about 3700. This product may be made by thecondensation reaction of mole parts of bound propylene oxide With 1 moleof glycerol. The resulting propoxylate may then be treated with toluenediisocyanate and is then condensed with propylene imine. The resultingproduct contains 3 aziridinyl radicals per mole, an imine content of0.65-0.67 meq./gram polymer and a viscosity of about 890 poises and ishereafter referred to as ITP63A. This material is dissolved in a 4:1

benzenedimethylformamide solvent mixture. The ITP-63A Dimensionalstabilization of wool fabricv by treatment with the imine-terminatedpolymer of Example I and a polyamine Samples of plain weave woolenfabric in the ready-to-dye state were treated with mixtures of TIP-63Aand polyamines by padding from a 4:1 benzene-DMF solution. Theequivalent ratio of the imine.-terminated polymer to the amineco-reactant was 1:1, with the weight ratio as specified below. Thestepsof thetreatment Were as described in Example 1, except that the wetpickup was about I In the pad solution Percent Total j Percent Percentreag. Percent Amine amine PIP-63A OWF W.G.

Sample:

B Tetraethylene 0.11 3.49 4.42 4.0

pentamine. C Dietl ylenetri- 0.10 3.50 4.24 5 5 amine. D 1,3-diamin0pro-0.11 3. 4 9 4. 28 6.1

pane. E 1,6-diaminohexane- 0.16 3. 44 4. 31 t 6.2

The properties of the treated samples were as follows:

' Percent shrinkagc- ,7

10L Stifii a ness' W, --Flex abn, Rcflcc-t W F mg.cm. eycles llli tance13 EXAMPLE I11 Dimensional stabilization of woolen fabric with apropylene imine-terminated polymer employed in Example I and apolycarboxylic acid 14 (4% toluene, 0.4% Triton X-100 nonionic surfaceactive agent, 95.6% water) at room temperature for 5 minutes, thenwashed in water at 100 (F. for minutes, rinsed in cold water and driedon frames.

The properties of the treated samples were as follows:

Percent shrinkage Percent 5L 10L polymer Percent Stifiness, Flex. abr.Fabric OWF W.G. W F W F mg.cm. res., cycles Plain weave, woolen RTD* 3.7 3. 1 2. 5 2. 5 2. 5 3. 0 136 600 Untreated RTD 19. 0 17. 5 28. 5 26. 0103 475 Twill weave, woolen RTD. 3. 6 2. 7 1. 5 2. 0 1. 5 2. 0 203 775Untreate 20. 0 18. 5 27. 5 26. 0 164 575 Twill weave, woolen dyed green3. 6 2. 9 5. 0 5. 5 6. 5 6. 5 171 400 Untreated dyed 23. 5 20. 0 30.025. 5 105 525 Twill weave, worsted. 3. 2 2. 5 3. 5 3. 5 176 3, 400Untreated RTD 33. 5 30.0 165 4,190

"RTD Ready-to-Dye.

Example II was repeated, but polycarboxylic acids were EXAMPLE V used asco-reactants in the treating solution in place of the aminoco-reactants.

In the pad solution Percent Polyear- Percent poiytotal boxyliccarboxylic Percent reag. Percent acid acid ITP-63A OWF W.G.

The properties of the treated samples were as follows:

Percent shrinkage Dimensional stabilization of woolen fabrics of variousweaves using the polymer employed in Example I Samples of plain .weaveand twill weave woolen fabric Dimensionally stabilizing and impartingoil repellency to woolen fabrics Samples of dyed plain weave 100% woolenand twill weave worsted fabric were treated with a mixture of ITP- 63Aaqueous emulsion (preparation of the emulsion is described in ExampleIV) and of a fluorochemical emulsion, Scotchgard FC-208 (product ofMinnesota Mining & Manufacturing Co.), which is a nonionic latex of a'modified fluorinated acrylic polymer of the type polyperfluoroalkylacrylate using a laboratory padder and setting the rolls at such apressure as to give 90116% wet pickup. The fabric samples so treatedwere framed and dried at 150 F., then cured at 320 F. for 5 minutes in aforced-draft oven. The cured fabric samples were washed and dried in themanner described in Example IV. The properties of the treated sampleswere as follows:

TREATMENT Percent Scotch- TESTIN G Percent shrinkage Oil Repellency 1L5L Stifi- Flex abr.

ness W, res, W 2 Dry W F W F mg.-cm. cycles Orig. 1L 5L 1 D .C.cleanings and of twill weave worsted fabric were treated with anGenerally, the above mentioned fluorochemical finishes aqueous emulsionof ITP63A.

The emulsion was. prepared by mixing 120 parts of a 50% xylene solutionof ITP-63A with 10 parts of the nonioni'c surface active agent,t-octylphenylnona(ethyleneoxy)ethanol (Triton X-100, a product of Rohm &Haas 'C0.), dissolved in 20 parts of water with stirring. The emulsionobtained in this manner was diluted with water to the desiredconcentration. The fabric samples were treated with the diluted emulsionusing a laboratory padder, setting the rolls at such a pressure to give80- 100% wet pickup.

The fabric samples so treated were framed to the original dimension anddried at 150 F., then cured for 5 minutes at 300 F. in a forceddraftoven. The cured fabare believed to be made from monomers having thebasic formula R CH OCOCH=CH where R can vary from C F to C F forexample.

EXAMPLE VI Hydroextraction of dimensionally stabilized woolen fabric ricsamples were rinsed in an aqueous toluene emulsion ner described inExample 1V.

15 The properties of the treated samples were as follows: is a linearpolyester (molecular weight of approximately 2100, made from a diol anda dibasic acid of the type Percent shrinkage shown in Formula IV)containing the following' imine Drying 1L 5L group attached to thebackbone: Percent'I'lP in the Percent Time in H bath IT ,OWF minutes W FW F 5 OCO NH CH3 g 3-; 33 ;-g 3-; g; 3-2, 1 118 22 2 2 8 2 3 2 at 1.8

8.5 5.0 14.5 12.5 (JHZ 1 A 5:4:1 DMF-toluene-acetone solution was usedto pre- EXAMPLE VII pare the treating solution used for the application.The Dyeing of woolen fabrics dimensionally stabilized with 21 22 2 fig i223 23 f if fl zg i i gg aqueous emulsion of polymers employed inExample y g lndicated below. IV

The treatment was earned out in the manner described Samples of twillweave 100% woolen fabric in readyin Example I. i to-dye state weretreated with an aqueous ITP-63A emulsion (percent polymer OWE: 4%)according to the pro- Percent Percent cedure described in Example IV.After the shrinkproofing Total pad Percent- Reag. Percent treatment, thesamples were dyed with 0.75% and 3.0% Amine solution ITP-43 OWF W0. DuPont Anthraquinone Blue SWF (C.I. No. 62055, C.I., Sample. I v Acid Blueacid dye and also with 0.75% capracyl Tetraethylene- 0.11 3.7 4.0 6.3Red 15B (Color Index name C.I. Acid Red 178) pref Q15 metallrzeddyestuff. In each case, untreated wool sarn :1 pm ples were dyed in thesame dye bath with the treated 25 :p noprosamples. Testing of thesamples before and after dyefi q 0.16 ing gave the following results: NH Percent shrinkage 5L 10L Res. to 81:15- Tensile flex abr., ness, ColorW F W F str., W W cycles ing.'crn

Sample: A-l, treated RID 3.0 3.5 20 900 231 11-2 untreated RID 22.5 22.527.0 25.0 20 775 142 Light Red 2.5 3.0 2.5 3.0 20 450 240 ..do 15.5 18.518.5 22.5 17 400 110 Dark Red... 2.0 2.5 2.0 2.5 10 415 231 do.. 18.010.0 22.5 23.5 17 325 167 Light 131115.... 1.5 1.0 1.5 1.5 21 575 218..do 15.5 17.5 20.0 23.5 20 575 147 Dark Blue 2.0 0.5 2.0 1.0 22 775 160E2, untreated .do 16.0 17.5 10.5 22.5 20 800 231 The depth of shade andthe brightness of color ob- The physical properties of the treatedsamples were as tained in dyeing the shrinkproofed and the untreatedsamfollows: 3 ples were fully comparable and the treated samples dyed asevenly as the untreated. 5

The colorfastness of the dyed samples shown in the preceding table wereas follows: In each case the 1 samples were dyed after shrinkproofingand the 2 samples were dyed in the untreated state.

NOTE .-S Satisfactory; U Unsatisfactory.

EXAMPLE VIII Dimensional stabilization of Woolen fabric with anothertype of imine-terminated polymer and a polyamine Samples of twill weave100% woolen fabric in the ready-to-dye state were treated with mixturesof an imineterminated polymer marketed by the Interchemical Corp. underthe trade name of ITP-43 and having an average molecular weight of about2600, and an aziridinyl content of about 0.65 meq./g., and with thepolyamines shown in the table as co-reactants. The ITP-43 polymerPercent Shrinkage-5L Flex Abr. Stirr- Res., ness-W, W V E Cycles rug-em.

XA L 1 Dimensional stabilization of woolen fabrics with theimine-terminated polymer of Example VIII and a polycarboxylic acidExample VIII was repeated :but, in place of thepolyamines,'polycarboxylic .acids wereused as co-react'ants with ITP-43.

Percent.- Pereent Polycar- Polycarbox- Total boxylic ylie acid in thePercent reag. Percent acid pad bath ITP-43 OWE W.G

17 EXAMPLE X Dimensional stabilization of a dyed wool fabric A 100-yd.length of 100% woolen fabric of -60-inch width, twill weave, dyed brightred, was treated by padng with an aqueous emulsion containing 8% of theITP-63A imine-terminated polymer. The wet pickup was 60%. The fabric wasdried on a frame, cured for 6 minutes at 275 F., thoroughly washed at110 F. in a nonionic detergent solution, dried and sheared to enhanceits appearance. The properties of the red fabric before and after theshrinkproofing treatment described are tabulated below:

Before After treatment treatment Count (W x F) 36 x 32 37 x 33 Percentshrinkage in relaxation (W x F). 5. x 4. 3 2. O x 2. Total after 1L .5 x7. 5 2.0 x 2. 5 Total after 5L 22 0x170 2.5x2.8 Total alter L. 25 0 x19. 5 3. 0 x 3.0 Tensile strength, W lbs 19 21 Tear strength, W lbs 2. 82. 7 Flex abr. res., cycles... 490 550 Stiffness, mg.cn 132 134 Weight(oz./sq. yd.) 7. 29 7. 48 Colorfastness:

To light:

20 hrs 5 5 40 hrs 4/5 4/5 To wash 4/5 4/5 To croeking' Dry- 5 5 T et 7i. 3 5

o perspna ion:

cid 3 4 Alkali 3 4 EXAMPLE XI Preparation of a polyfunctional compoundhaving 1) a polyester chain as its backbone and (2) terminall-aziridinyl radicals Isocyanate-terminated polyester, wherein v=34 andn is about 6.

l-aziridinyl-terminated polyester.

The isocyanate-terminated polyester used as the starting material had anisocyanate content of 9.5% and was obtained under the registeredtrademark of lsofoam L-128 from Isocyanate Products, Inc., Wilmington,Del.

A l-liter 3-neck flask equipped with a stirrer, a thermometer, a refluxcondenser, and a dropping funnel was charged with 100 grams (0.23equivalent based on isosolved in grams of methylene chloride.Ethylem'mine 10.7 grams, 0.25 equivalent), dissolved in 100 ml. ofmethylene chloride, was added dropwise to the stirred solution in theflask at 25 to 28 C. The addition was completed in 1 hour, and thereaction solution remained homogeneous. Stirring was continued for 5hours longer. Then solvent and unreacted ethylenimine were distilled offin vacuo, leaving behind the addition product, ethylenimine-terminatedpolyester, as a waxy solid.

The product was analyzed for aziridinyl content by a procedure modifiedafter that of Allan and Seaman, Anal. Chem., vol. 27, page 540 (1955).It was found to have an aziridinyl content of 1.73 milliequivalents pergram, as compared with 2.06 millieq./g. theoretically possible. Theconversion, based on aziridinyl activity, was 84%. The product was verysoluble in toluene and in N,N- dimethylformamide.

EXAMPLE XII Preparation of a polyfunctional compound having 1) apolyester chain as its backbone and (2) terminal Z-methyl-l-aziridinylradicals Isocyanate-terminated polyester as in Example XIPropylenimine-terminated polyester A l-liter 3-neck flask equipped witha stirrer, a thermometer, a reflux condenser, and a dropping funnel wascharged with 14.2 grams (0.26 equivalent) of propylenimine dissolved in50 ml. of methylene chloride. Isocyanate-terminated polyester (100grams, 0.23 equivalent) dissolved in ml. of methylene chloride was addeddropwise to the stirred solution at 25 to 28 C. (Theisocyanate-terminated polyester was of the same composition as that usedas starting material in Example XI, but both the order of addition andthe alkylenimine were different from those of Example XI.) The additionwas completed in 1 hour, and the reaction solution remained homogeneous.Stirring was continued for 5 hours longer. Then solvent and unreactedpropylenimine were distilled off in vacuo, leaving behind the additionproduct, propylenimine-terminated polyester, as a waxy solid.

Using the analytical method cited in Example XI, the product "was foundto have 1.60 milliequivalents of aziridinyl nitrogen per gram. Based onthat, the extent of conversion was'80%. This product was very soluble incyanate content) of isocyanate-terminated polyester dis- 75 toluene andin N,N-dimethylformamide.

19 EXAMPLE XIII HO(--CHzCH=CHCHz-)..OH Hydroxyl-terminated polybutadlene(u =60;l:5)

HaC

Isocyanate-terminated polybutadiene (VI) Second stage:

First-A 500-ml. flask equipped as in Example XIII was charged with 85.3grams of the hydroxyl-terminated polybutadiene dissolved in 50 grams ofmethylene chloride. Toluene diisocyanate (18.5 grams, 0.16 mole of NCOl-Aziridinyl-terminated polybutadiene The hydroxyl-terminatedpolybutadiene used as the starting material had a hydroxyl content of0.80 milliequivalent per gram, an iodine number of 395, and an averagemolecular weight of 325 0:25 0. The polymer was supplied under the tradename Poly B-D Liquid Resin R-lSM by Sinclair Petrochemicals, Inc. Priorto use, the resin was kept in vacuo in a slowly rotating flask forseveral hours to strip off moisture.

The first stage of the process consisted of converting thehydroxyl-terminated polybutadiene into isocyanateterminatedpolybutadiene. A 2-liter 3-neck flask equipped with a stirrer, athermometer, a gas inlet tube, and a dropping funnel was charged with200 grams of the hydroxyl-terminated polybutadiene dissolved in 200grams of methylene chloride. Toluene diisocyanate (43.6 grams, 0.25 moleof 2,4 and 2,6 isomers in the ratio of 80/20) was added while a streamof nitrogen was passed into the solution and the temperature wasmaintained at 20 C. After the addition, the solution was stirred at -28C. for 8 hours.

Next, the second stage of adding terminal l-aziridinyl radicals wascarried out. Ethylenimine (12.9 grams, 0.30 mole), dissolved in 100grams of methylene chloride, was added dropwise to the stirred solution.The addition was completed in 2.5 hours, during which time thetemperature of the reaction was maintained at 25 C. The solution wasstirred for 4 hours longer. Then solvent and unreacted ethylenimine weredistilled off in vacuo. The product (223 grams) which remained was alightbrown viscous liquid.

Using the analytical method cited in Example XI, the product was foundto have 1.00 milliequivalent of aziridinyl per gram, as compared with0.97 millieq./g. expected. The product, ethylenimine-terminatedpolybutadiene, was very soluble in toluene, benzene, tetrahydrofuran,and carbon tetrachloride.

EXAMPLE XIV Preparation of a polyfunctional compound having (1) Apolybutadiene chain as its backbone and (2) Terminal2-methyl-1-aziridinyl radicals H H H C-CH; H3CC\ (H) /C-CHa joined as inum i Example x111 CH2 H2O CH2 Propylenimine-terminated polybutadiene 2,4and 2,6 isomers in the ratio of 80/20) was added slowly while a streamof nitrogen was passed into the solution and the temperature wasmaintained at 20 C. After the addition, the solution was stirred at 25to 28 C. for 16 hours.

Second.Propyleniminc (6.70 grams, 0.18 mole), dissolved in 50 grams ofmethylene chloride, was added dropwise to the stirred solution during a3-hour period. The solution was stirred for 4 hours longer. Then solventand unreacted propylenimine were distilled off in yacuo. The productwhich remained was a light-brown 'iquid.

Using the analytical method cited in Example XI, the product was foundto have 0.90 milliequivalent of aziridinyl nitrogen per gram, ascompared with 0.97 millleqJg. theoretically possible. The product,propylenimine-terminated polybutadiene was very soluble in toluene.

EXAMPLE XV Enhancement of surface characteristics of :30 rayon-woolfabric by imine-terminated polymer Plain-weave fabric woven from a 70:30blend of highmodulus high-tenacity rayon and Wool was treated with thepropylenimine-terminated polymer identified in Example I so that thereagent applied was 4%, based on the weight of the fabric. The fabricspecimen so treated was framed at the original dimensions and dried at150 F. (in approximately 10 minutes), then cured for 6 minutes at 275 F.The cured fabric was scoured to remove unreacted reagent by using anemulsion for mulated from 4 parts of toluene, 0.4 part of Triton X-100(emulsifying agent identified in Example IV), and 95.6 parts of water.Then the fabric specimen was again framed to the original dimensions anddried. The following results, along with those on an untreated fabricsample used as the control, clearly show that the treatment enhancedsurface characteristics, and even improved the strength somewhat.

22 framed at the original dimensions and dried at 150 F.

Flex abras.

Shrinkage, percent Curing ten niq (time= 5 mins.)

All samples were cured for 5 minutes. The cured fabric was rinsed intoluene, then in p-dioxane and finally in water containing 0.4% TritonX-l (identified in Example IV). The samples were again framed to theorigiand rayon was treated with the propylenrmme-terminated naldimensions and dried. Excellent dimensional stabilizapolymer identifiedin Example I so that the reagent ap- Total add-0n, percent on ight offabric 3,523,750 21 EXAMPLE XVI Control imparted on shrinkage andfuzziness to 50:50

tion was achieved, as borne out by the following results:

Percentages on wt. of bath Wet pickup, we

Reagent TEPA percent wool-rayon fabric by imine-terminated polymerPlain-weave fabric woven from a 50:50 blend of wool 5055555505550 0LLLLZL&LZZ4 W 000000000000 5 5 55 5 4 om25 4 &2

Shrinkage, percent Curing F. 5L (time= 5 mins.) W F EXAMPLE XVIII andredrying were those of Example XV. The following DimensionalStablhzatlon of Woolen fabric by treatment results, and those of theuntreated fabric sample used as the control, show much more satisfactorycontrol of shrinkage and of fuzziness for the treated specimen.

Total add-on, percent on tem weight on fabric withpropylenimine-terminated polybutadiene (A) Pad bath solventzToluenedimethylformamide (1:1).Samples of plain-weave woolen fabric in theready-to-dye state were treated with solutions of various concentrationsof the reagent prepared in Example XIV, namely propylenimine-terminatedpolybutadiene. In the Fumness treatment of some of the samples,tetraethylenepentamine F rating (TEPA) was used as a co-reactant.

4 The procedure followed that of Example XVII. 2 Results tabulated belowshow that this i-mine-terminated polymer also provided excellent controlof shrinkage.

Percentages on weight of bath Wet pickup, Reagent 'IEPA percentShrinkage, percent (Tumble dried at 105 F.)

plied was 3.5% based on the weight of the fabric. Conditions of framing,drying, curing, scourmg, reframmg,

Treated specimen. Untreated control.

555000050 LLLLZZLLZ 3 0550550 5 ZLLomZLZLH 005555050 LLLOJLLLL5 ghtratio of toluene-dimethyl- Flex abras.

B) Pad bath solventzToluene dimethylformamide (5 :1).--The proceduredescribed under part A was followed,'except that a 5:1 wei formamide wasused instead of the 1:1 ratio, and lower concentrations of the reagentwere used to establish its ng efficiency. As before, shrinkage controlwas impressive, as shown by the following results.

Total Curing Shrinkage, percent Percentages on add-on, temp,

wt. of bath Wet percent on F. 5L

pickup, weight of (time= Reagent TEPA percent fabric fimins.) W

EXAMPLE XVII Dimensional stabilization of woolen fabric by treatmentwith ethylenimine-ter-minated polybutadiene Samples of plain-weavewoolen fabric in the readyto-dye state were treated with solutions ofvarious conshrinkproofi centrations of the reagent prepared in ExampleXIII Sample:

EXAMPLE XIX Dimensional stabilization of woolen fabric by treatment withethylenimine-terminated polyester Samples of plain-weave woolen fabricin the ready-todye state were treated with solutions of various concenofa laboratory padder. After padding, the fabric was trations of thereagent prepared in Example XI, namely,

namely, ethylenimine terminated polybutadiene. Concentrations and otherdetails were shown in the accompanying table. In preparing certain ofthe samples, tetraethylenepentamine (TEPA) was also used in the padbath. The solvent was toluene-dimethylformamide (1:1). Solutions wereapplied to the fabric samples by means 23 ethylenimine-terminatedpolyester. In the treatment of some of the samples, a co-reactant wasused, viz., tetraethylenepentamine (TEPA). The procedure followed thatof Example XVII. Excellent shrinkage control resulted, as the followingdata show.

24 EXAMPLE XXII Improvement of dyed acrylic-wool blends byimineterminated polymer, particularly with respect to control offuzziness and resistance to abrasion Each of three 30-yard lengths ofcolored fabrics repre- Total Shrinkage, percent Percentages on add on,Curing weight of bath Wet percent on temp., F L L ckup, weight of (t e=Reagent TE PA percent fabric 5 mins.) W F W F 5.0 None 133 6. 6 2751.0 1. 5 1. 5 2. 5 5. 0 None 133 6. 6 325 0. 5 2. 0 1. 0 2. 0 5. 0 0. 5133 6. 6 275 1. 5 3. 0 2. 0 3. 0 5. 0 0.5 131 6. 5 325 1. 0 2.0 1. 5 3.03.0 None 132 4. 0 275 1. 5 3. 0 2.0 3. 5 3. 0 None 130 4. 0 325 1. 0 3.0 1. 5 3. 5 3. 0 0.5 134 4.0 275 1. 0 3. 0 2. 5 4. 0 3. 0 0. 5 13. 0 3.9 325 1. 5 2. 5 2. 0 4. 0 23. 5 22. 5 30. 0 29. 0

EXAMPLE XX sentmg various acryl1c-wool blends identified 1n the ac-Dimensional stabilization of woolen fabric by treatment withpropylenimine-terminated polyester Samples of plain weave woolen fabricin the ready-todye state were treated with solutions of variousconcentrations of the reagent prepared in Example XH, namely,propylenimine-terminated polyester. In the treatment of some of thesamples, a co-reactant was used, viz., tetraethylenepentarnine (TEPA).The procedure followed that of Example XVII. The following results showthat superior shrinkage control was obtained:

companying table was padded with a dispersion formulated as follows:First, ITP-63A (the imine-terminated polymer described in Example I) wasdissolved in an equal weight of xylene, and a thick emulsion wasprepared by mixing parts of that solution with 20 parts of a 2:1 blendof water and Triton X-100 (identified in Example IV). Hence, theconcentration of ITP-63A in the'thick emulsion was 40%. Next, anapproximately 3.9% dispersion of ITP-63A was made by blending pounds ofsaid thick emulsion and gallons (approximately 830 pounds) of water.

Total Curing} Shrinkage, percent Flex abras. Percentages en add-on,temp., 1 (15 lb. 1: Stifiness, wt. of bath Wet percent on F. 5L 10L211).), mg.-em., pickup, weight of (time: No L, No L Reagent TEPApercent fabric 5 mins.) W F W F (warp) (warp) 3. 0 114 3.4 275 1. 5 1.03. 0 1.5 850 505 2. 0 115 2. 3 275 3. 5 0. 5 5. 5 2. 5 900 370 1. 0 1. 2275 7. 0 3. 5 12. 5 7. 5 725 160 3.0 111 3. 3 275 2. 0 0. 5 3.0 0. 5 1,050 625 2. 0 110 2. 2 275 1. 5 None 3. 0 1. 5 900 355 F 1. 0 111 1. l275 4. 5 0. 5 6.5 3. 5 825 210 Untreated control 27 25 32 31 850 100EXAMPLE XXI Dimensional stabilization of woolen garments in thereadyto-wear condition by shrinkproofing agents applied asperchloroethylene solutions Wet pickup around 50%, the pad pressurebeing 16 tons and the speed 25 yards per minute. For the combined stepof drying-curing, conditions were 300 F. for 4.83 minutes. Next, thelengths were scoured at 100 F. for 15 minutes in a dispersion formulatedfrom 4 parts of toluene, 0.4 part of a nonionic dispersant,nonylphenylpoly(ethyleneoxy)ethanol (Triton N-l00, a product of Rohm &Haas (10.), and 95.6 parts of water. Then the lengths of fabric wererinsed until no foam was evident. The goods were dried and given dryfinishing by shearing off the fuzz and semidecating (pressing bysteaming between pieces of fabric). Results on the treated acrylic-Tumble Time of Solids, drying Percent of shrinkhydro- Wet percent(curing) Sweater proofer in perchloroextraction, plekup, on weight time,Other conditions applied prior to measurspeermen ethylene secondspercent of fabric minutes ing process shrinkage W 10% of ITP-63A 7 15415.4 60 15-min. wash in toluene water 4:96 at 105 F., then tumble-dried.X 10% of ITP-63A 8 103 10. 3 60 Same as for W. Y 10% of ITP-63A 5 23423. 4 60 1 wash at F.; then tumble-dried.

Laundering shrinkage, percent, after 10L and Process shrinkage, percenttumble drying I Back Bottom Sleeve Back Bottom Sleeve Sweater speeunenBand length wldth length Chest Band length width length Chest 12. 7 10.6 None 5. 6 None None 2. 4 +0. 8 2. 4 None. 10. 7 9. 9 (l0 5. 6 NoneNone 2. 4 None 2. 4 Do. 5.7 4.3 2.3 +0.7 1.4 2.3 +3.5 Do.

wool blends as well as'those on untreated controls are tabulated below.The values show a consistent improvement in fuzziness rating incomparison with the corresponding untreated control specimen, both priorto laundering and after .12 launderings. Wash-and-wear ratings were notadversely affected. Resistance to flex abrasion and flat frosting remaineither unchanged or were improved by the treatment.

utes. The procedures of scouring, drying, shearing, and semidecatingwere similar to those of Example XXII. As to properties, creaseretention and wash-and-wear rat ings (on pressed specimens) wereimproved over those of similar fabrics processed in a conventional way.Other values on the treated polyester-wool blends, along with controldata, are tabulated below, and show the substantial improvement broughtabout by the imine-terminated Flat frosting Resistance to flex FuzzinessWash-and-wear rating (2.5-lb., abrasion, cycles (l-lb. rating rating1,200 cycles) head, 4-lb. toggle) No L Composition of dyed fabric No L12 L 1 L 12 L No L Web Rupture 55% acrylic/45% wool 5 4 4. 5 3. 5 5 525800 55% acrylic/45% wool, untreated controL. 3 3 4. 5 3. 5 5 500 800 65%acrylic/30% wool/5% rayon 3-4 3 4. 3 3. 4 225 525 65% acrylic/30% wool/%rayon, untreated eontrol- 1 1 4. 5 3. 5 3 150 300 70% acrylic/30% wool 43-4 3. 5 3. 5 5 375 575 70% acrylic/30% wool, untreated control 2 2 3. 53. 5 5 275 475 EXAMPLE XX-III polymer on each polyester-wool blend.

Control of fuzz and abrasion of dyed polyester-wool blends byimine-terminated polymer Each of four 60-yard lengths of colored fabricsof two different polyester-wool blends identified in the accompanyingtable was padded with a dispersion formulated as follows. Anapproximately 5.4% dispersion of ITP-63A was made by blending 130 poundsof the thick emulsion (40% ITP- 63A) recorded in Example XXII and 100gallons (approximately 830 pounds) of water. Wet pickup wasapproximately 50%, the pad pressure being 12 tons. Speed was 25 yardsper minute. For the combined step of drying-curing, conditions were 300F. for 4.5 min- EXAMPLE XXIV Each of eight lengths of fabrics of fourkinds of blends of synthetic fibers with wool as identified in theaccompanying table was padded with a solution formulated as follows.

An approximately 5.5% dispersion of ITP-63A was made by blending 113pounds of the thick emulsion ITP63A) recorded in Example XXII and 85gallons (approximately 705 pounds) of water. Pad pressure was 12 tons,and speed was 15 yards per minute. For the com- Re i t t flex ij gfiffg40 blned step of drying-curing, conditions were 275 F. for ggg g 3 ig f7.5 minutes. The procedures of scouring, drying, shearg ing, andsemidecating for the acrylic-wool blends were Co pos t on of dyed fabrwsNo L 10 L Web Rupture similar to those of Example XXII, but thepolyester-wool 55% polyester/% W001, 6m oL/Sq, blends were singed beforesemidecating. Singeing means Y H 650 285 45 burning off the freeprojecting fibers from the surface of 55% polyester/45% wool, 6.900z./sq. h 1

yd,,unt eated comm; 2 34 525 125 t e 0 0th, leaving it smooth and bare.Upon evaluation, D Y 1 4 H 375 185 it was found that crease retentionand wash-and-wear 55%, b'dfitiii kfii bbi,i'if/if. ratings (on pressedspecimens) were improved over 10$"..ii3idli32iiiii' 8265755" 2 3 150those of similar fabrics processed in a conventional mand ihi '1 4 5 1,050 275 ner. Other data on the treated blends of synthetic fibers 707olyester/307 wool 6.82 oz.lsq.

e r: untreated o H 3 650 135 and wool, dyed as Well as undyed, togetherwith control 70% polyester/30% wool, 5 500 175 data, are tabulatedbelow. Definite lmprovement was efyd 70% polyester/30% wool, 4.57oz./sq. fected by the imine terminated polymer on each wool yd.,untreated control 3 4 425 110 containing blend. (Control samples weredyed but otherwise untreated.)

Laundering shrinkage, percent (10-inch markings machine wash, Resistanceto 105 F. tumble dry, low

flex abrasion setting) cycles (1 lb X et 4-lb.) No L, 5L 10L Yardagepickup, web --1- Composition of fabric State treated percent W F W F 557polyester/457 wool. Dyed 35 52 650 1.0 1.0 1.0 1.5 Control Untreated 5251.5 3.0 1.5 a. 5 Undye 35 51 775 1.5 o. 5 1.5 0.5 70% polyester/30%w0ol.. "I, Dyed 35 50 875 0. 5 1. 0 0. 5 1. 5 Contr0l Untreated 775 0. 52. 0 0. 5 1 3. 5 Undyed.- 50 1,050 0.5 None 0.5 None 55% acrylic/45%wool Dyed 50 56 650 1. 5 1. 5 2. 5 8.0 Control..- Untreated 525 2. 5 3.5 2. 5 4. 0 Undyed--. 50 55 725 1.0 2.0 1. 5 2.5 acrylic/30% wool Dyed50 57 575 1. 5 0. 5 1. 5 1. 0 ControL-.. Untreated 425 2. 5 2.5 2. 5 2.5Undyed.-. 5o 50 500 1.5 1.0 1.5 1.5

27 EXAMPLE XXV Preparation of a polyfunctional compound having (1) apolyester chain as its backbone, and (2) terminal 2-(1-aziridinyl)ethoxy groups Isocyanate-terminated polyester, wherein v=3 to4 and n=about 6 -i5 C. 4-methyl-m-phenylene diisocyanate (35.4 grams,0.203 mole) dissolved in 50 grams of dichloro- Starting materials andthe procedure were similar to methane was added. The temperature wasallowed to those of Example XI except as follows: The weight ofdichloromethane was 330 grams instead of 100 grams. Instead ofethylenimine, (l-aziridine)ethanol (20.7 grams, 0.238 mole) was addeddropwise to the stirred solution at 20 to C. The addition was completedwithin 1 hour. The reaction solution remained homogeneous. One-half hourafter termination of the addition, the infrared absorption band wasdevoid of the isocyanate band (4.3 to 4.5 microns). Analysis revealed anaziridinyl content of 0.15 equivalent per 100 grams of solid(calculated, 0.197 eq./100 g.). The solution was miscible withdimethylformarnide.

EXAMPLE XXVI Preparation of a polyfunctional compound having (1) apolytetramethyleneoxy chain as its backbone, and (2) terminal2-(1-aziridinyl)ethoxy groups First stage:

NCO

On the average, x=about 26 in Example XXVI, and about 13 in ExamplesXXVII and XXV-III OCN NCO ICTIT, an isocyanate-terminated intermediatehaving a backbone derived from a polytetramethyleneoxy chain Secondstage:

rise to 25 C. during 1 hour. The reaction mixture was stored atapproximately 5 C. for several days.

Next, the second stage of adding terminal 2-(-aziridinyl)ethoxy radicalswas carried out. (1-aziridine)ethanol (17.4 grams, 0.20 mole) was addeddropwise to 19/20 of the original solution obtained from the firststage. The stirred solution contained 0.19 equivalent of N=C=O[determined by a modification of the dibutylamine procedure of W.Siefken, Liebigs Annalen der Chemie, vol. 562, page 100 (1949)]. Theaddition was completed in 0.5 hour, during which time the reactiontemperature was kept at 26- -2 C. The solution was stirred for 2 hourslonger, after which time the infrared spectrum was devoid of theisocyanate band at 4.3 to 4.5 microns. The solu-' tion had an aziridinylcontent of 0.076 equivalent per 100 grams of solid (0.084 eq./100 g.,calculated). The solution was micible with dimethylformamide.

EXAMPLE XXVII A preparation similar to Example XXVI, but of lowermolecular weight The chemical equations of Example XXVI applied, exceptthat x, the degree of polymerization, was about 13 on the average. Thepolytetramethylene ether glycol used in Example XXVII had an averagemolecular weight of approximately 1020.

In the first stage, 200 grams (0.393 equivalent of hydroxyl) ofpolytetramethylene ether glycol and 68.4 grams (0.393 mole) of4-methyl-m-phenylene diisocyanate were allowed to interact underconditions similar to those of Example XXVI. Two days later, theisocyanate content 2-(l-aziridinyl)ethoxy-terminatedpolytetramethyleneoxy chain I The polytetramethylene ether glycol usedas the starting material had an average molecular weight ofapproximately 1980. The polymer was marketed under the trade namePolymeg by Quaker Oats Co. 0

The first stage of the process consisted of convertrng was 0.40equivalent (theoretically 0.393 equivalent).

In the second stage, 93% 0f the isocyanate-terminated intermediate wasallowed to react with 34.8 grams (0.4 mole) of (1-aziridine)ethanol in amanner similar to that described in Example XXVI. The aziridinyl contentof the product was 0.13 equivalent per grams of solid (0.14 eq./100 g.,calculated).

29 EXAMPLE XXVIII In the second stage, 0.26 equivalent of theisocyanate- A preparation similar to Example XXVII but having terminatedintermediate was allowed to react with 11.3

grams (0.26 mole) of ethylenimine in a manner similar to that describedin Example XXVI. The aziridinyl content the Chemical equation pp y tothe fi Stage, was found to be 0.14 equivalent per 100 grams of solid seeExample XXVI, x=about 13 on the average. h i ll 0,14 ,/100

Second stage:

(ICTIT) 2H2NOH2OH2NCH2CH2 terminal 2-(1-aziridinyl)ethylamino groups 0I'm I'm O=(i3CHzGHzNCH2CHz 0=d-goHioHeNoHioHe 2-(1-aziridinyl)ethylaminoterminated polytetramethyl- EXAMPLE XXX eneoxy chain 7 v 7 n Apreparation having (1) a complex polyester chain as In the first stage,the isocyanate-terminated intermedi- Its backbone and (2) termmall'azmdmyl groups ate. (ICTIT) having a backbone derived from apolytetra- First stage:

( 0.164 eq./100 g. calculated.)

HO CHzOHzOH Isoeyanate-terrninated polyester (starting material ofEXAMPLE XXV) methyleneoxy chain was prepared in a manner similar toICTIP, an isocyanate-terminated intermediate having a that of ExampleXXVII from polytetramethylene ether backbone derived from a complexpolyester chain Second stage:

40 The first stage of the process was carried out as fol- 1 col hav-n anavera 5 molecular Wei ht of a roxi lows. A mixture of 6.82 grams ofethylene glycol (0.11 ig g g pp mole) and 75 grams of dichloromethanewas added quick- In the Second stage, 031 equivalent of the isocyanately to a stirred solutlon at 0 C. consisting of 200 grams terminatedintermediate which was 79% of the original 9 dichloromethane and 200grams ((1446 q v t o amount obtained in the first stage was allowed toreact Y of y h nated polyester identlfied with 33.5 grams of1-(2-aminoethyl)aziridine dissolved 111 Example Stlfrlng Was eontlmledas the reaction i grams f dichloromethane in a manner Similar to mixturewas allowed to warm to room temperature. After that described in ExampleXXVI. The aziridinyl content 2 e the lsoeyanate content e e constant at0.24 was found to be 0.17 equivalent per 100 grams of solid. equlvalent(calculated, 0-226 q U- For the second stage, a solution of 6.4 grams(0.149 50 mole) of ethylenimine and 50 grams of dichloromethane EXAMPLEXXIX was added dropwise within 1 hour at room temperature Pre aration ofa 1 functional compound having (1) a to of -P the product equivalfint rsidue of ethoig la ted glycerol as the central portion of of lsocyanate),obtamed m the first Stage- After a its molecule, and (2) terminall-azidinyl groups of 1 the Infrared .spectrum. was devold ti 1S0-cyanate band. The reaction solution had an azridinyl cont 1 Adductglycerol and ent of 0 1 equivalent per 100 grams of solid (0.12 eq./

ethylene oxide1z32' 3(OCN )2C6H3*CHS 3HNCHZCH2 100 g., calculated;theoretically 0.103 eq. of the desired approximately, by moles W Wproduct per 100 grams of solids). The desired product has a complexpolyester backbone terminated at both ends CHKOCECHQP 60 of the moleculeby l-aziridinyl groups.

H(0CHzOHz) 15523132 EXAMPLE XXXI HZ(OCH2OHZ)I H 1! 3 Dimensionalstabilization of woolen fabric by treatment with the product of Example)Q(V wherein x+x+z=approximately 32. Samples of 100% woolen fabric in aplain Weave and The ethoxylatedglycerol used as starting material hadwelghlhg Ounce? Pe q e y Were treated at an average molecular weight of1495. In the first stage, eefdlngh) the tluantltatlve detalls ill theaccompanying 200 grams of the ethoxylated glycerol and grams 70 tableWith. SOlUtlODS Of the PI'OdllCt Of Example X)(V. (0.402 mole) of4-rnethyl-m-phenylene diisocyanate were A 38% solution of the product indichloromethane Was allowed to interact under conditions similar tothose of diluted by dimethylformamide to give the percentages ExampleXXVI. By analysis at the end of the reaction OWB shown in theaccompanying table. Solutions were period, the isocyanate content wasfound to be 0.42 equivapplied by means of a laboratory padder. Afterpadding;

alent (theoretically 0.402 equivalent). the samples were framed at theoriginal dimensions and 31 dried at approximately 50 C. All samples werecured for minutes. The cured fabric was rinsed in dimethylformamide,then in a 0.1% aqueous solution of p- 1,1,3,3 -tetramethylbutylphenoxynona(ethyleneoxy)etl1- 32 EXAMPLE XXXIII Dimensionalstabilization of woolen fabric by treatment with the product of ExampleXXVII anol again framed to the original dimensions, and dried. 5 Theprocedure of Example XXXII was repeated using Shrinkproofing evaluationwas excellent and durable, as is as the reagent the product of ExampleXXVII, a lowerevident from the evaluation results in the accompanylngmolecular-weight polymer than had been used in Example table. Thepolymer was reactive because of amine-type XXXII. A 60% solution of theproduct in dichlorol-aziridinyl groups terminating the chain, the centerpormethane was diluted with dimethylformamide to give tion of which wasapolyester. the percentages OWB shown in the accompanying table.

Warp flex Shrinkage, percent Product of Example Actual abrasion re- WarpGreen XXV, percent Cure weight slstance stlflfilter 5L 10L temp, gain,0.5 X 2 lb ness, reflect OWB WPU OWF 0 percent cycles mg.crn. ance W F WF Sample:

A-l 5.5 127 7.0 135 4.94 815 1,814 53 1.5 0.5 2.0 0.5 5.5 129 7.1 1634.38 675 1,241 56 1.5 None 2.0 0.5 2.6 121 3.1 135 2.92 815 651 58 1.50.5 2.5 0.5 13-2 2.6 127 3.3 163 2. 74 515 811 55 1.5 None 2.5 0.5Untreated Control 700 125 62 20.5 16.5 27.5 26.0

EXAMPLE XXXII Dimensional stabilization of woolen fabric by treatmentwith the product of Example XXVI Samples of the woolen fabric identifiedin Example Warp flex Green Shrinkage, percent Product of Example Actualabrasion Warp filter XXVIII, percent Cure weight resistancestifireflect- 5L mp., gain, 0.5 x 2 lb., ness, ance,

OWB WPU OWF 0 percent cycles mg.e1n. percent W F 3. 120 4. 1 135 3. 9 1,100 700 63 2. 5 2. 0 3. 40 116 3. 9 163 3. 9 975 495 63 4. 0 1. 5 1. 1192. 0 135 3. 2 1, 025 599 64 1. 0 1. 5 1. 70 118 2. 0 163 3. 2 1, 375 49963 1. 5 1. 5 0. 123 1. 0 135 2. 4 1, 175 320 63 1. 5 2. 0 D-2 0. 35122 1. 0 163 2. 3 950 328 62 1. 5 2. 0 Untreated control. 815 107 65 22.5 11. 0

XXXI were treated according to the general procedure of that examplewith the following variations: The reagent was the product of ExampleXXVI. A 54% solution of it in dichloromethane Was diluted withdimethylformamide to give the percentages OWB shown in the accompanyingtable. After padding, samples (18 by 17 inches) were dried atapproximately 65 C. Curing was for 5 minutes, and other quantitativedetails are in the accompanying table. Excellent shrinkproofing resultedfrom the use of the reactive polymer having a backbone made up ofrepeating tetramethyleneoxy units, the molecular chain being terminatedby amine-type l-aziridinyl groups. Even at low concentration, thereagent was very effective.

EXAMPLE XXXIV Dimensional stabilization of woolen fabric by treatmentwith the product of Example XXVIII Warp flex Green Shrinkage, percentProduct 01 Example Actual abrasion Warp filter XXV III, percent Cureweight resistance stifireflect- 5L emp., gain, 0.5 x 2 1b., ness, ance,

OWB WPU OWF 0 percent cycles mg.-cm. percent W F 3. 3 4. 0 5. 4 1, 51063 1. 5 1. 5 3. 3 119 3. 9 163 5. 3 915 685 62 1. 0 1. 0 1. 7 120 2. 0135 2. 6 975 387 64 1. 5 1. 5 1. 7 119 2. 0 163 2. 9 725 429 63 1. 5 1.5 0. 9 121 1. 1 135 1. 7 750 288 64 4. 0 1. 5 D2 0. 9 118 1. 1 163 1. 7825 307 64 3. 5 2, 5 Untreated control. 815 107 65 22. 5 11. 0

mg resulted over a good range of concentratlons with It 1s understoodthat various other modifications will thls reactive polymer. be apparentto and can readlly be made by those skilled v p Warp flex GreenShrinkage, percent Product of Example Actual abrasion Warp filterXXVIII, percent Cure weight resistance stifireflect- 5L temp., gain, 0.5x 2 1b., ness, ance,

OWB WPU OWF percent cycles ing-cm percent; W F

5.00 118 5.9 135 -7.0 1,475 2,000 63 1.5 0.5 5. 00 117 5. 9 163 6. 8 l,250 1, 700 62 l. 5 0. 5 3. 33 114 3. 8 135 3. 8 1, 175 1, 300 63 1. 0 0.5 3. 33 110 3. 8 163 3. 5 1, 025 1, 200 62 1. 5 0. 5 1. 67 111 1. 9 1352. 1 925 600 62 2. 5 (0. 5) 1. 67 115 1. 9 163 2. 1 850 400 61 2. 5 None0. 84 114 1. 0 135 1. 4 850 380 64 4. 5 (0. 5) 0.84 117 1.0 163 1.4 775430 62 4.5 (0. 5) 815 107 65 22. 5 11. 0

' Percentages in parentheses are the opposite of shrinkage. l

EXAMPLE XXXV Dimensional stabilization of woolen fabric by treatmentwith the product of Example XXIX A procedure similar to that of ExampleXXXII was followed, using as the product of Example XXIX, a polymerWhose central moiety came from ethoxylated glycerol, and havingamide-type l-aziridinyl terminal groups. A 51% solution of the productin dichloromethane was diluted with dimethylformamide to give thepercentages OWB shown in the accompanying table. Good results onshrinkproofing are evident.

Warp flex Green Shrinkage, percent Product of Example Actual abrasionarp filter XXVIII, percent Cure weight resistance stifireflect- 5Ltemp., gain, 0.5 x 2 1b., ness, ance,

OWB WPU OWF 0 percent cycles mg.cm. percent W F 129 6. 6 135 7. 8 1, 200490 62 2. 0 0. 5 124 4. 2 135 6. 0 1, 000 425 62 2. 0 0. 5 121 2. 1 1353. 5 975 295 63 4. 5 0. 5 D 120 1. 0 135 2. 5 1, 050 260 64 6. 5 NoneUntreated control- 815 107 65 22. 5 11. 0

EXAMPLE XXXVI Dimensional stabilization using the product of Example XXXA procedure similar to that of Example X)Q(I was followed, using theproduct of Example XXX, a polymer whose central moiety was mainly apolyester, and whose terminal groups were amide-type l-azinidinylgroups.

teinaceous material a polyfunctional compound of the formula m is ininteger of from 2 to 3, A is selected from the group consisting of Az,

The product was diluted wlth dimethylformamlde to and CEHZBAZ give thepercentages OWB shown In the accompanylng a is an integer from 1 to 4,table. All samples were cured for 5 minutes at approxi- AZ is mately 163C. Upon evaluation, good control of shrink- I age was obtained, as isapparent from the accompanying. .60 N

' table.

TABLE T0 EXAMPLE XXXVI I Shrinkage, percent Product of Example XXX,percent Actual Abrasion resls- Warp stifi- 1L 5L weight tance 0.5 x 2ness, mgr OWB WPU OWF gain% 1b., cycles cm. W F W F Wool fabric sample:

4.4 4.0 875 258 3.5 0.5 4.0 None 2.1 3.2 825 277 3.0 0.5 3.5 0.5 Controluntreated 900. 132 10.5 3.0 21.5 12.5

35 wherein R R R are selected from the group consisting of H and alkylhaving from 1 to 4 carbon atOrns, J is selected from the groupconsisting of (g) (C Hawk- 2 a has the meaning given above,

x, y and z independently are integers of from about 1 to 100,

u is an integer of from about 6 to 100,

n is an integer of from 2 to 6,

v is an integer of from about 3 to 80,

q is an integer of from 3 to 5,

r is an integer of from 2 to 35, and

L is a divalent alicyclic radical of 3 to 20 carbon atoms, C to Calkylene, or C to C alkylene having the chain interrupted by one to tenO, -S, or groups in which R is H or alkyl having 1 to 5 carbon atoms,

Q is selected from the group consisting of C H e a(- 3), z e 4 2-,CGH4CGH4 10 6 a said polyfunctional compound being applied from a liquidmedium and heating the proteinaceous material having 36 acids of 2 to 12carbon atoms and polyalkylenepolyamines of 4 to 20 carbon atoms and 2 to5 nitrogen atoms.

7. A process as claimed in claim 1 wherein Q is 8; The process of claim6 wherein about 0.5 to about 2.0 equivalents of co-reactant arepresentuforeach aziridinyl group present and the pH of the liquid mediumranges between about 30 to about 9.0. i

9. The compound of the structure:

A is selected from the group consisting of 10. The compound of thestructure:

polyfunctional compound applied thereto until the desired wherein v isan integer ranging from 3 to 4, and

dimensional stabilization takes place.

2. A process as claimed in claim 1' wherein said proteinaceous materialis wool.

3. A process as claimed in claim 1 wherein said polyfunctional materialis dissolved in an inert organic solvent.

plied thereto is heated at a temperature of about 100 to 200 C.

6. A process as claimed in claim 1 wherein, in addition to saidpolyfunctional compound there is applied to said proteinaceous materiala coreactant selected from n is an integer ranging from 2 to 8.

11. The compound of the structure:

l r Nfi-OKCH2)40lx(CH2)40%N-@CH3 CH 1? /CH2 O=CgCH2OH2N\ I CH2 CH2wherein x is an integer ranging from 5 to 40.

12. The compound of the structure:

I onaoomom 0$[JN@CH CH H-(OCH2CHz) o i 2 N-CN H2(OOH2OH2)Z H H o CH2 3the group consisting of saturated aliphatic dicarboxylic whereinx+y+z=approximately 32.

3,523,750 37 38 13. The compound of the structure: wherein x+y+z=50, andsaid polyfunctional compound is applied from an aqueous emulsion.

wherein v is an integer ranging from 3 to 4, and n is an integer rangingfrom 2 to 8.

14. The compound of the structure:

NH CH2 o=o on oomonm oomcmN on, on,

wherein v is an integer ranging from 2 to 6, and n is an integer rangingfrom 4 to 8.

15. The compound of the structure:

NH /CH2 N CH2 O=(EOCH2CH2N\ O=0CH2CH2N\l CH7 Ha wherein x is an integerranging from 5 to 40. 18. A process as claimed in claim 6 wherein thepoly- 16. A process as claimed in claim 6 wherein said polyfunctionalcompound is of the structures:

0 0 O O I I (@OK-CHa-MO X-CHzQv--OM-CHz-h-Oy HN- -CH3 HIL- -CH a on, on,

NHG0N\Jj v NHOON H: CH2

functional compound is of the structure: a.

H wherein n is an integer of from 2-to 6; q is an integer CH2(0CsHe)x 0ON CH; g of from 3 to 5; and r is an integer of from 2 to"35.

Ekwcm)y a 19. A process as claimed in claim 6 wherein the polyfunctionalcompound is of the structure: Hz(OCaHo)u H H HO:C\ o cm N-i: C-N v I iH,

1120 IIIH t I a H wherein x+y+z=50, the co-reactant is a polyalky lenepolyamine, and perchloroethylene is present as an inert organic solvent.wherein u is an integer of from about 6- to 100*. v

17. A process as claimed in claim 6 wherein said poly- 20. A process asclaimed in claim ,6 wherein the polyfunctional compound is of thestructure: functional compound is of the structure:

H C -CH H (CLHflOCSHI) 0 "N s/ H-(OCaHah O II (I} N\ I H2(OC:H0). 1 OH:3

on; (I? 0 on; I

N-C (LL-N/ l 112 EN NH OH:

wherein n is an integer of from 2 to 6, and v is an integer of from 3 to80.

21. A process as claimed in claim 6 wherein the polyfunctional compoundis of the structure:

wherein u is an integer of from about 6 to 100.

22. A process as claimed in claim 6 wherein the polyfunctional compoundis of the structure:

NH +=o CH2 {i=0 /CH3 OCHzOHzN l OCHzCHzN\l wherein v is an integer offrom about 3 to 80, and n is an integer of from 2 to 6.

23. A process as claimed in claim 6 wherein the polyfunctional compoundis of the structure: 40 t H H oH3-@N( -o om)401x(ong)io- N-@-ona 0 0 l N/CH2 NH /CH2 O=(L/OCH2CH2N l O=( OCHzCH2N\ H; CH2

wherein x is an integer of from about 1 to 100.

24. A process as claimed in claim 6 wherein the polyfunctional compoundis of the structure:

H H CHa-@Nfi-OKCH2)40];(CH2)4OfiN-@CH:1

l 0 0 l IIIH /CH2 IIIH /CH: 0=C-NCH;0H;N O=GNCH2CH2N CHa CH2 wherein xis an integer of from about 1 to 100.

25. A process as claimed in claim 6 wherein the polyfunctional compoundis of the structure:

60 H onuoomomn- -ooN-@-om I oil- 0011011 i n on 001 1 013 ll \i 2 Z 2 z0 H 3 wherein x+y+z=approximately 32.

26. A process as claimed in claim 1 wherein the polyfunctional compoundis of the structure:

CH O-C-N N-CO Grimm-o (onnno C-N- CH3 l 1 I H l: II] It I I /CH2 1HN-(I?N I C Ha

